U.S. patent number 8,637,427 [Application Number 12/918,582] was granted by the patent office on 2014-01-28 for adsorptive composition and adsorptive molded article.
This patent grant is currently assigned to Toyo Seikan Kaisha, Ltd.. The grantee listed for this patent is Daisuke Hiratsuka, Anzu Kasai, Kazuaki Ohashi, Shigeru Suzuki. Invention is credited to Daisuke Hiratsuka, Anzu Kasai, Kazuaki Ohashi, Shigeru Suzuki.
United States Patent |
8,637,427 |
Ohashi , et al. |
January 28, 2014 |
Adsorptive composition and adsorptive molded article
Abstract
An adsorptive composition comprising a composition that contains
at least one kind of fatty acid metal salt of any one of Ni, Cu or
Co and ultrafine metal particles having a plasmon absorption over
300 to 700 nm. The adsorptive composition has an excellent effect
of adsorbing both amine-type smelling components and
sulfur-containing smelling components.
Inventors: |
Ohashi; Kazuaki (Kanagawa,
JP), Kasai; Anzu (Kanagawa, JP), Hiratsuka;
Daisuke (Osaka, JP), Suzuki; Shigeru (Osaka,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Ohashi; Kazuaki
Kasai; Anzu
Hiratsuka; Daisuke
Suzuki; Shigeru |
Kanagawa
Kanagawa
Osaka
Osaka |
N/A
N/A
N/A
N/A |
JP
JP
JP
JP |
|
|
Assignee: |
Toyo Seikan Kaisha, Ltd.
(Tokyo, JP)
|
Family
ID: |
41016107 |
Appl.
No.: |
12/918,582 |
Filed: |
February 26, 2009 |
PCT
Filed: |
February 26, 2009 |
PCT No.: |
PCT/JP2009/053558 |
371(c)(1),(2),(4) Date: |
August 20, 2010 |
PCT
Pub. No.: |
WO2009/107720 |
PCT
Pub. Date: |
September 03, 2009 |
Prior Publication Data
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|
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Document
Identifier |
Publication Date |
|
US 20110028313 A1 |
Feb 3, 2011 |
|
Foreign Application Priority Data
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Feb 29, 2008 [JP] |
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2008-050984 |
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Current U.S.
Class: |
502/402; 502/401;
502/400 |
Current CPC
Class: |
B01J
20/0233 (20130101); B01J 20/3246 (20130101); B01J
20/0225 (20130101); C08K 3/08 (20130101); A61L
9/01 (20130101); B01D 53/02 (20130101); C08K
5/098 (20130101); B01J 20/28042 (20130101); B01J
20/261 (20130101); B01J 20/3007 (20130101); B82Y
30/00 (20130101); B01J 20/28026 (20130101); B01J
20/02 (20130101); B01J 20/0237 (20130101); B01J
20/28007 (20130101); B01J 20/3236 (20130101); B01J
20/262 (20130101); B01J 20/223 (20130101); B01J
20/28011 (20130101); C08K 2201/007 (20130101); B01J
2220/46 (20130101); B01D 2257/90 (20130101); B01D
2253/20 (20130101); B01D 2257/304 (20130101); B01D
2253/34 (20130101) |
Current International
Class: |
B01J
20/26 (20060101); B01J 20/02 (20060101) |
Field of
Search: |
;502/400,401,402 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1066825 |
|
Jan 2001 |
|
EP |
|
1452188 |
|
Sep 2004 |
|
EP |
|
1882511 |
|
Jan 2008 |
|
EP |
|
1-156053 |
|
Jun 1989 |
|
JP |
|
9-75434 |
|
Mar 1997 |
|
JP |
|
10-183207 |
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Jul 1998 |
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JP |
|
2002-126511 |
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May 2002 |
|
JP |
|
2006-109902 |
|
Apr 2006 |
|
JP |
|
2006-348213 |
|
Dec 2006 |
|
JP |
|
03/045449 |
|
Jun 2003 |
|
WO |
|
2006/080319 |
|
Aug 2006 |
|
WO |
|
2008/029932 |
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Mar 2008 |
|
WO |
|
Other References
Search report from E.P.O. that issued with respect to patent family
member European Patent Application No. 09716152.5, mail date is
Jul. 28, 2011. cited by applicant.
|
Primary Examiner: Hendrickson; Stuart
Assistant Examiner: Berns; Daniel
Attorney, Agent or Firm: Greenblum & Bernstein,
P.L.C.
Claims
The invention claimed is:
1. A resin composition containing adsorptive ultrafine metal
particles, comprising a resin composition that contains at least
one kind of fatty acid metal salt of any one of Ni, Cu or Co in a
low-density polyethylene and ultrafine silver particles having an
average particle diameter of 1 to 100 nm, a plasmon absorption from
300 to 700 nm and an infrared absorption peak at 1518 cm.sup.-1
stemming from the bond between an organic acid component and a
metal, wherein said organic acid is a saturated fatty acid having 3
to 30 carbon atoms, and a silver salt of said organic acid and at
least one kind of the fatty acid metal salt of any one Ni, Cu or Co
are heated and mixed in the low-density polyethylene to form said
ultrafine silver particles and to render the organic acid present
on the surfaces of said ultrafine silver particles so that the
ultrafine silver particles and the fatty acid metal salt of any one
of Ni, Cu or Co are dispersed in the low-density polyethylene.
2. An adsorptive molded article comprising a layer that contains at
least one kind of fatty acid metal salt of any one of Ni, Cu or Co
in a low-denstiy polyethylene, and a layer that contains ultrafine
silver particles having an average particle diameter of 1 to 100 nm
a plasmon absorption at 300 to 700 nm and an infrared absorption
peak at 1518 cm.sup.-1 stemming from the bond between an organic
acid component and a metal in the low-density polyethylene, wherein
said organic acid is a saturated fatty acid having 3 to 30 carbon
atoms, and a silver salt of said organic acid is heated and mixed
in the low-density polyethylene to form said ultrafine silver
particles and to render the organic acid present on the surfaces of
said ultrafine silver particles, and at least one kind of fatty
acid metal salt of any one of Ni, Cu or Co is heated and mixed in
the low-density polyethylene so as to be dispersed therein.
Description
TECHNICAL FIELD
This invention relates to an adsorptive composition containing a
fatty acid metal salt. More specifically, the invention relates to
an adsorptive composition capable of adsorbing smelling components
of either amine-type smelling components or sulfur-containing
smelling components, and to an adsorptive molded article.
BACKGROUND ART
There have heretofore been proposed a variety of deodorizing
substances for use being added to thermoplastic resins to impart
deodorizing function to the molded articles thereof.
For instance, active carbon, inorganic filler such as porous
zeolite or sepiolite, and titanium oxide utilizing photo-catalytic
action, are capable of deodorizing a wide range of smelling
components and have heat resistance lending themselves well for
being melt-kneaded with the thermoplastic resin (patent document
1).
There has, further, been proposed a deodorant using ultrafine metal
particles, such as a deodorant using, as an effective component, a
colloidal solution of ultrafine metal particles obtained by
reducing a metal ion-containing solution (patent document 2).
Further, the present applicant has proposed a resin molded article
in which are dispersed ultrafine metal particles having an average
particle diameter of 1 to 100 nm by heat-molding a mixture of a
fatty acid silver salt or a fatty acid gold salt and a resin at a
temperature higher than a temperature at which the fatty acid metal
salt starts thermally decomposing but at a temperature lower than a
temperature at which the resin thermally deteriorates (patent
document 3). The applicant has, further, discovered that the
ultrafine metal particles exhibit performance for adsorbing
offensively smelling components such as methyl mercaptane, etc. and
volatile organic compounds (hereinafter "VOC") such as
formaldehyde, etc. (patent document 4). Patent document 1:
JP-A-9-75434 Patent document 2: JP-A-2006-109902 Patent document 3:
JP-A-2006-348213 Patent document 4: WO2006/080319
DISCLOSURE OF THE INVENTION
Problems that the Invention is to Solve
However, the deodorants utilizing a porous substance exhibit their
deodorizing effect upon adsorbing smelling components, and are
accompanied by a problem in that their deodorizing effect
extinguishes if the adsorption sites are saturated. Further, in
order to improve dispersion property, the inorganic filler must use
a dispersant at the time when it is melt-kneaded with a
thermoplastic resin. Therefore, there remains a problem in that the
adsorption sites in the surfaces of the inorganic filler are
covered with the resin or the dispersant causing the deodorizing
effect to decrease conspicuously.
Further, the deodorant utilizing the photo-catalytic action has a
problem in that the surface of the titanium oxide must have been
irradiated with ultraviolet rays at all times to decompose and
deodorize the smelling components.
Moreover, ultrafine metal particles and, particularly, the
adsorptive ultrafine particles containing ultrafine silver
particles, exhibit excellent adsorption performance for methyl
mercaptane and sulfur-containing offensively smelling components,
such as hydrogen sulfide and methyl sulfide, but are not still
satisfactory with regard to adsorbing amine-type offensively
smelling components, such as dimethylamine and trimethylamine.
It is, therefore, an object of the present invention to provide an
adsorptive composition which exhibits excellent adsorption effect
for either the amine-type smelling components or the
sulfur-containing smelling components free from the above-mentioned
problems possessed by the conventional deodorants.
Another object of the present invention is to provide an adsorptive
molded article capable of adsorbing not only sulfur-containing
smelling components but also amine-type smelling components such as
trimethylamine, and having a very excellent effect for deodorizing
offensively smelling components.
Means for Solving the Problems
According to the present invention, there is provided an adsorptive
composition comprising a composition that contains at least one
kind of fatty acid metal salt of any one of Ni, Cu or Co and
ultrafine metal particles having a plasmon absorption from 300 to
700 nm.
In the adsorptive composition of the present invention, it is
desired that:
1. The fatty acid metal salt and the ultrafine metal particles are
contained in a resin or in a solution;
2. The ultrafine metal particles have an infrared absorption peak
near 1518 cm.sup.-1 stemming from the bond between the organic acid
and the metal;
3. The ultrafine metal particles have an average particle diameter
of 1 to 100 nm; and
4. The ultrafine metal particles comprise silver.
According to the present invention, further, there is provided an
adsorptive molded article having a layer containing at least one
kind of fatty acid metal salt of any one of Ni, Cu or Co and a
layer in which are dispersed ultrafine metal particles having a
plasmon absorption ever from 300 to 700 nm.
In the adsorptive molded article of the present invention, it is
desired that:
1. The ultrafine metal particles have an infrared absorption peak
near 1518 cm.sup.-1 stemming from the bond between the organic acid
and the metal;
2. The ultrafine metal particles have an average particle diameter
of 1 to 100 nm; and
3. The ultrafine metal particles comprise silver.
As described above, the present inventors have discovered that
ultrafine metal particles such as of silver have excellent
adsorption performance. Though the ultrafine silver particles
exhibit performance for adsorbing sulfur-containing components such
as methyl mercaptane and the like which are representative
offensively smelling components, however, they are not capable of
effectively adsorbing amine-type smelling components.
Upon containing a fatty acid metal salt of at least any one of Ni,
Cu or Co, however, the adsorptive composition of the present
invention becomes capable of effectively adsorbing amine-type
smelling components.
The above action and effect of the invention will also become
obvious from the results of Examples appearing later. That is, the
one obtained by blending copper stearate with silver stearate
(Example 1), the one obtained by blending cobalt stearate with
silver stearate (Example 2) and a laminated film obtained by
laminating a film of a composition containing silver stearate on a
film of a composition containing copper stearate (Example 3), all
work to deodorize amine-type smelling components and sulfur-type
smelling components such as methyl mercaptane, and are, therefore,
capable of effectively deodorizing offensively smelling
components.
On the other hand, when use is made of a metal stearate comprising
silver, manganese or zinc as a metal component, the amine-type
smelling components can be deodorized up to a maximum of only 30%
(Comparative Examples 1 to 4).
Effects of the Invention
The adsorptive composition of the present invention effectively
adsorbs amine-type smelling components due to the fatty acid metal
salt of Ni, Cu or Co and effectively adsorbs sulfur-containing
smelling components due to the fine metal particles having a
plasmon absorption ever from 300 to 700 nm.
By molding an article having a layer containing at least one kind
of fatty acid metal salt of any one of Ni, Cu or Co and a layer in
which are dispersed ultrafine metal particles having a plasmon
absorption over 300 to 700 nm, further, offensively smelling
components of both amine-type smelling components an sulfur-type
smelling components can be deodorized more effectively.
MODE FOR CARRYING OUT THE INVENTION
(Fatty Acid Metal Salts)
The metals of the fatty acid metal salts for effectively adsorbing
amine-type smelling components used in the invention are Co, Cu and
Ni as described above. Among them, Co and Cu are desired.
The fatty acid used for the fatty acid metal salt of the invention
is a fatty acid having 3 to 30 carbon atoms and may be either
saturated or unsaturated. Examples thereof include caproic acid,
caprylic acid, capric acid, lauric acid, myristic acid, palmytic
acid, oleic acid, linoleic acid, linolenic acid, stearic acid and
arachidinic acid. Particularly, stearic acid and myristic acid are
desired. Upon having a branch and an increased number of carbons,
the fatty acid by itself is capable of adsorbing smelling
components making it possible to further improve the deodorizing
effect. A plurality of number of fatty acids may be used.
Desirably, there is used a straight-chain saturated fatty acid
having 12 to 22 carbon atoms. If the number of carbon atoms is less
than 12, the fatty acid highly dissolves in water decreasing the
yield of the fatty acid metal salt which is the product. If the
number of carbon atoms is not less than 23, the fatty acid
dissolves less in water which is the starting material making it
difficult to prepare the fatty acid metal salt.
In the present invention, in particular, it is desired to use a
fatty acid metal salt having a water content of less than 200 ppm.
Upon mixing it with the resin and heat-molding the mixture,
therefore, there is obtained a resin composition having a favorable
color tone and particularly excellent ability for adsorbing
offensively smelling substances.
As the ultrafine metal particles having a plasmon absorption from
300 to 700 nm capable of effectively adsorbing sulfur-type smelling
components, further, there can be exemplified Ag, Au, In, Pd, Pt,
Fe, Nb, Ru, Rh and Sn. Among them, Ag is particularly desired.
These metal components may be used in a single kind, as a mixture
or as an alloy.
For these fatty acid metal salts, too, it is desired to use the
same fatty acid components as those for the above-mentioned fatty
acid metal salts.
In the present invention, in particular, it is desired to use fatty
acid silver. This enables the formation of ultrafine metal
particles having a bond between the fatty acid and the metal in the
resin or in the coating at the time of heating such as molding or
firing the coating, making it possible to excellently adsorb
sulfur-type smelling components.
It is desired that the ultrafine metal particles have a maximum
diameter of not larger than 1 .mu.m and an average particle
diameter, particularly, in a range of 1 to 100 nm.
The average particle diameter referred to in this specification is
an average value of the individual metal particles assuming that
there is no gap among the metal particles.
In the present invention, it can be confirmed that the ultrafine
metal particles have an effect of adsorbing the sulfur-type
smelling components from the phenomenon of plasmon absorption in
that the ultrafine metal particles absorb light of wavelengths over
a range of 300 to 700 nm.
The above ultrafine metal particles are the adsorptive ultrafine
metal particles having an infrared ray absorption peak near 1518
cm.sup.-1 stemming from the bond between the organic acid and the
metal, having high surface activity and large surface areas, having
excellent reactivity to the sulfur-type smelling components such as
methyl mercaptane, higher adsorption rate and larger adsorption
amount than those of the ordinary particles, and expressing
excellent adsorption effect. Moreover, due to the presence of
organic acid on the surfaces of the ultrafine metal particles, the
ultrafine metal particles are very favorably dispersed in the resin
and, at the same time, effectively suppress the decomposition of
the resin, preventing a decrease in the molecular weight of the
resin so that the moldability will not be impaired.
(Adsorptive Resin Compositions)
The adsorptive composition of the present invention can be a resin
composition containing, in a resin, at least one kind of fatty acid
metal salt of any one of Ni, Cu or Co and ultrafine metal particles
having a plasmon absorption from 300 to 700 nm. Upon heat-molding
the resin composition, there can be obtained an adsorptive molded
article of a desired form.
As the resin to be blended with the fatty acid metal salt, there
can be used any known thermoplastic resin that can be melt-molded,
like olefin resins such as low-, intermediate- or high-density
polyethylene, linear low-density polyethylene, linear
ultra-low-density polyethylene, isotactic polypropylene,
syndiotactic polypropylene, propylene/ethylene copolymer,
polybutene-1, ethylene/butene-1 copolymer, propylene/butene-1
copolymer and ethylene/propylene/butene-1 copolymer; polyester
resins such as polyethylene terephthalate, polybutylene
terephthalate and polyethylene naphthalate; polyamide resins such
as nylon 6, nylon 6,6 and nylon 6,10; and polycarbonate resin.
In the adsorptive resin composition of the present invention, it is
desired that the resin has an oxygen permeability coefficient of
not less than 1.0.times.10.sup.-4 ccm/m.sup.2dayatm. This makes it
possible to easily adsorb smelling components and to further
improve deodorizing performance.
According to the present invention, it is particularly desired to
use a polyethylene for the adsorptive resin composition.
Depending on the use, further, the adsorptive resin composition of
the present invention can be blended with various blending agents
that have been known per se. such as filler, plasticizer, leveling
agent, viscosity-imparting agent, viscosity-reducing agent,
stabilizer, antioxidant and ultraviolet ray absorber according to
known recipe.
It is desired that the adsorptive resin composition of the present
invention is blended with the fatty acid metal salt of any one of
Co, Cu or Ni in an amount of 0.01 to 10 parts by weight per 100
parts by weight of the resin. If the amount is smaller than the
above range, the adsorptive effect is not obtained to a sufficient
degree. If the amount is larger than the above range, on the other
hand, the moldability may decrease, which is not desirable.
It is, further, desired that the fatty acid metal salt of Co, Cu or
Ni used for the adsorptive resin composition is in the form of fine
particles having an average particle diameter of 1 to 100 .mu.m,
and is kneaded with the resin.
On the other hand, the other fatty acid metal salt such as fatty
acid silver used for forming ultrafine metal particles having a
plasmon absorption is added desirably in an amount of 0.01 to 10
parts by weight per 100 parts by weight of the resin, and the
obtained ultrafine metal particles desirably have an average
particle diameter of 1 to 100 nm.
The adsorptive resin composition of the invention can be subjected
to a known melt molding such as two-roll method, injection molding,
extrusion molding or compression molding to finally obtain the
adsorptive resin-molded articles in shapes that meet the use, such
as granules, pellets, films, sheets, containers, etc.
The conditions for heat-treating the resin composition vary
depending on the kinds of the resin and the fatty acid metal salt
that are used, and cannot be definitely defined. It is, however,
desired that the resin composition is heat-treated at a temperature
at which the fatty acid metal salt that forms the ultrafine metal
particles having a plasmon absorption undergoes the thermal
decomposition in the resin but at which the resin is not thermally
deteriorated.
The temperature at which the fatty acid metal salt undergoes the
thermal decomposition may be higher than a temperature at which the
fatty acid metal salt starts decomposing but does not necessarily
have to be higher than the temperature at which the fatty acid
metal salt starts decomposing. In practice, the temperature is
affected by the heat of shearing due to the screw or by the
residence time in addition to the setpoint temperature of the
extruder. It is, therefore, desired to conduct the heat treatment
by adjusting the working conditions such as residence time, heating
time, rotational speed of the screw, etc.
Further, the adsorptive molded article comprising the adsorptive
resin composition of the invention may by itself constitute an
adsorptive resin molded article but may also assume a multi-layer
structure including a layer that contains at least one kind of
fatty acid metal salt of any one of Ni, Cu or Co and a layer in
which are dispersed ultrafine metal particles having a plasmon
absorption from 300 to 700 nm. As the ultrafine metal particles
having a plasmon absorption from 300 to 700 nm, there can be
exemplified Ag, Au and Cu, and Ag is particularly desirable.
The resin molded article obtained from the adsorptive resin
composition of the invention has excellent deodorizing performance,
exhibits adsorption performance just as the resin is molded into an
article, and excels in productivity.
(Adsorptive Coating Compositions)
The adsorptive composition of the present invention can be a
coating composition containing, in a coating material, at least one
kind of fatty acid metal salt of any one of Ni, Cu or Co and
ultrafine metal particles having a plasmon absorption from 300 to
700 nm, which is capable of forming a coating. The coating
composition is applied onto the base body and is fired to form an
adsorptive coating on the base body.
It is desired that the fatty acid metal salt of Ni, Cu or Co is
added in an amount of 0.01 to 10 parts by weight per 100 parts by
weight of the coating component (resin component). If the amount
thereof is smaller than the above range, the deodorizing effect is
not obtained to a sufficient degree. If the amount thereof is
larger than the above range, on the other hand, the coating
formability may decrease, which is not desirable.
Like in the case of the above resin composition, further, a fatty
acid metal salt such as fatty acid silver is added to form
ultrafine metal particles having the plasmon absorption so that the
coating expresses the above-mentioned effect.
As the fatty acid metal salt such as the fatty acid silver, etc.
like in the above resin composition, it is desired that the other
fatty acid metal salt is added in an amount of 0.01 to 10 parts by
weight per 100 parts by weight of the coating component (resin
component).
As the coating component to which the fatty acid metal salt is to
be added, there can be used various components provided they are
capable of forming a coating upon heating. For example, though not
limited thereto only, there can be used a known coating composition
such as acrylic coating material, epoxy coating material, phenol
coating material, urethane coating material, polyester coating
material or alkyd resin coating material.
The conditions for heat-treating the coating composition vary
depending upon the kinds of the coating component and the fatty
acid metal salt that are used, and cannot be definitely defined.
The coating composition, however, must be heat-treated under the
conditions of a temperature range in which the fatty acid metal
salt for forming the ultrafine metal particles having the plasmon
absorption undergoes the thermal decomposition in the coating
material but in which the coating component is not thermally
deteriorated for 60 to 600 seconds.
The coating obtained from the adsorptive coating composition of the
invention has excellent deodorizing performance, exhibits
adsorption performance just as the coating is formed, and excels in
productivity.
(Adsorptive Dispersion Solutions)
The adsorptive composition of the invention can be an adsorptive
dispersion solution containing, in a dispersion medium, at least
one kind of a fatty acid metal salt of any one of Ni, Cu or Co and
ultrafine metal particles having a plasmon absorption of from 300
to 700 nm.
The adsorptive dispersion solution can be used by being sprayed or
applied onto, or having been soaked in, the dwelling-related
members such as floors, walls, curtains, carpets, etc., fibrous
products such as of air conditions, woven fabrics, nonwoven
fabrics, etc., and the filtering members such as masks, filters,
etc.
As the dispersion medium used for the adsorptive dispersion
solution of the invention, a polyhydric alcohol can be favorably
used. It is desired that the polyhydric alcohol has a boiling point
higher than a temperature at which the fatty acid metal salt
undergoes the thermal decomposition in the dispersion medium, and
its examples include polyethylene glycol, diethylene glycol and
glycerol. Here, however, the polyethylene glycol is particularly
preferably used.
The polyethylene glycol preferably has an average molecular weight
in a range of 200 to 20000 and, particularly preferably, 400 to
10000. Further, a plurality of kinds of polyethylene glycols having
different molecular weights may be used being mixed together.
In the adsorptive dispersion solution of the invention, it is
desired that the fatty acid metal salt of Ni, Cu or Co is added to
the dispersion medium in an amount of 0.1 to 20% by weight and,
particularly, 1 to 5% by weight. If the amount of the fatty acid
metal salt is smaller than the above range, the adsorption
performance is not attained to a sufficient degree. If the amount
thereof is larger than the above range, on the other hand, the
dispersion thereof may decrease, which is not desirable.
It is, further, desired that the fatty acid metal salt such as
fatty acid silver for forming ultrafine metal particles having the
plasmon adsorption is added in an amount of 0.01 to 5% by
weight.
Desirably, further, an antioxidant is added as a protection agent.
Addition of the antioxidant prevents the thermal deterioration at
the time of heating.
As the antioxidant to be used, though not limited thereto only,
there can be exemplified known ones such as tocopherols (vitamin
E), hindered phenol-type antioxidant, phosphorus-type antioxidant
and ethylene bisstearic acid amide. Particularly desirably, Irganox
1010 (registered trade mark, produced by Chiba Specialty Chemicals
Co.) can be used. The antioxidant is desirably added to the
dispersion medium in an amount of 0.01 to 20% by weight.
The dispersion solution of the present invention can be prepared by
adding, to a dispersion medium, the fatty acid metal salt of any
one of Co, Cu or Ni, the fatty acid metal salt for forming
ultrafine metal particles having the plasmon absorption and, as
required, an antioxidant, and stirring and mixing them together
while heating them at a temperature at which the fatty acid metal
salt for forming the ultrafine metal particles having the plasmon
absorption undergoes the thermal decomposition in the dispersion
medium but lower than the boiling point of the solution. The
heating time differs depending upon the kind of the dispersion
medium that is used and the amount of the metal organoate that is
added, and cannot be definitely defined, but is desirably 1 to 1800
seconds and, particularly, 5 to 300 seconds. After heated and
mixed, the dispersion solution is cooled down to room temperature
and is filtered. Thus, the free fatty acid is removed from the
dispersion solution, and the adsorptive dispersion solution of the
invention is obtained.
The dispersion solution obtained by the production method of the
invention can by itself be used as an adsorptive (deodorant) but
is, desirably, used being diluted with a solvent.
The solvent used for the dilution may be, though not limited
thereto only, water such as purified water or ion-exchanged water;
lower alcohols such as methanol, ethanol, propanol, isopropanol and
butanol; general modified alcohols such as those modified with
methanol, those modified with benzole, those modified with triol,
those modified with methyl ethyl ketone, those modified with
denatonium benzoate and those modified with perfume; modified
alcohols such as ethylene glycol monoethyl ether, chloroform,
diethyl carbonate, ethyl acetate, ethyl propionate, ethyl butyrate,
hexane, and ethyl ether for industrial use; and glycol-type
solvents such as ethylene glycol monobutyl ether, diethylene glycol
monobutyl ether, propylene glycol monomethyl ether, propylene
glycol monopropyl ether, propylene glycol monobutyl ether,
propylene glycol diethylene glycol monobutyl ether, dipropylene
glycol ethylene glycol monobutyl ether, ethylene glycol monophenyl
ether, and triethylene glycol monophenyl ether. These solvents may
be used alone or in a combination of two or more kinds.
The present invention preferably uses a low-boiling solvent having
a boiling point of not higher than 100.degree. C., such as water or
ethanol and, particularly preferably uses an aqueous solution
containing ethanol at a concentration of 1 to 30%.
EXAMPLES
Calculating the Deodorizing Ratio
1. Measuring the Concentration of Offensively Smelling Substance of
When Not Deodorized.
By using a micro syringe, offensively smelling substances, i.e.,
dimethylamine and methyl mercaptane each in an amount of 5 .mu.L
were injected into 500-mL glass bottles purged with a nitrogen gas
and sealed for their mouth portions with rubber plugs, so adjusted
that their concentrations were 10 ppm, and were left to stand at
room temperature (25.degree. C.) for a whole day. After left to
stand for a whole day, detector tubes (manufactured by Gas-Tech
Co.) were inserted in the bottles to measure the concentrations of
the remaining offensively smelling substances, which were regarded
as the concentrations (A) of the offensively smelling substances of
when not deodorized.
2. Measuring the Concentrations of Offensively Smelling Substances
After Deodorized.
A film obtained by blending a thermoplastic resin with a fatty acid
metal salt was cut into two square pieces each side measuring 50
mm, and the pieces were hung in the 500-mL glass bottles purged
with the nitrogen gas and sealed with the rubber plugs. Next,
offensively smelling substances, i.e., dimethylamine and methyl
mercaptane each in an amount of 5 .mu.L were injected therein by
using the micro syringe so that the concentrations in the bottles
were adjusted to be 10 ppm, and were left to stand at room
temperature (25.degree. C.) for a whole day. After left to stand
for a whole day, the detector tubes (manufactured by Gas-Tech Co.)
were inserted in the bottles to measure the concentrations of the
remaining offensively smelling substances, which were regarded as
the concentrations (B) of the offensively smelling substances after
deodorized.
3. Calculating the Ratio of Deodorizing Offensively Smelling
Substances.
A value obtained by subtracting the concentration (B) of
offensively smelling substances after deodorized from the
concentration (A) of offensively smelling substances of when not
deodorized, was divided by the concentration (A) of offensively
smelling substances, and was expressed as the deodorization ratio
in percentage.
1. Confirming the Plasmon Absorption by Using a
Spectrophotometer.
The film containing ultrafine metal particles was measured for its
absorbance by using a spectrophotometer (UV-3100PC manufactured by
Shimazu Seisakusho Co.) to make sure the presence of plasmon
absorption of from 300 to 700 nm.
Example 1
A low-density polyethylene resin was blended with copper stearate
(II) and silver stearate as fatty acid metal salts each in an
amount of 0.5% by weight, and was extruded by using a biaxial
extruder at an extrusion-molding temperature of 220.degree. C. to
prepare a single-layer film (thickness of 50 .mu.m).
The obtained single-layer film was measured for its spectral
transmission factor, and the presence of plasmon absorption and the
ratio of deodorizing offensively smelling substances were
calculated.
Example 2
A single-layer film was prepared in the same manner as in Example 1
but adding cobalt stearate (II) and silver stearate as fatty acid
metal salts each in an amount of 0.5% by weight, and the presence
of plasmon absorption and the deodorizing ratio were
calculated.
Example 3
A low-density polyethylene resin of a first layer was blended with
copper stearate (II) as a fatty acid metal salt, and a low-density
polyethylene resin of a second layer was blended with silver
stearate as a fatty acid metal salt each in an amount of 0.5% by
weight. The two layers were coextruded by using a biaxial extruder
at an extrusion-molding temperature of 220.degree. C. to prepare a
two-layer film (thickness of 50 .mu.m).
Next, the presence of plasmon absorption and the deodorizing ratio
of the film were calculated in the same manner as in Example 1.
Comparative Example 1
Silver stearate was used as the fatty acid metal salt, and the
presence of plasmon absorption and the deodorizing ratio were
calculated in the same manner as in Example 1.
Comparative Example 2
Manganese stearate (II) was used as the fatty acid metal salt, and
the presence of plasmon absorption and the deodorizing ratio were
calculated in the same manner as in Example 1.
Comparative Example 3
Zinc stearate (II) was used as the fatty acid metal salt, and the
presence of plasmon absorption and the deodorizing ratio were
calculated in the same manner as in Example 1.
Comparative Example 4
Manganese stearate (II) was added to the first layer as the fatty
acid metal salt in an amount of 0.5% by weight, silver (average
particle diameter of 4.5 .mu.m) was added to the second layer in an
amount of 0.5% by weight, and the presence of plasmon absorption
and the deodorizing ratio were calculated in the same manner as in
Example 3.
TABLE-US-00001 TABLE 1 Methyl First layer Second layer
Dimethylamine mercaptane Presence Layer Base Fatty acid Base Fine
deodorizing deodorizing of plasmon constitution resin metal salt
resin particles ratio ratio absorption Ex. 1 single LDPE *1 -- --
80% 98% yes layer *2 Ex. 2 single LDPE *3 -- -- 65% 98% yes layer
*2 Ex. 3 2 layers LDPE *1 LDPE *6 75% 98% yes Comp. single LDPE *2
-- -- 20% 98% yes Ex. 1 layer Comp. single LDPE *4 -- -- 30% 10% no
Ex. 2 layer Comp. single LDPE *5 -- -- 20% 30% no Ex. 3 layer Comp.
2 layers LDPE *4 LDPE *7 30% 20% no Ex. 4 *1: copper stearate, 0.5
wt % *2: silver stearate, 0.5 wt % *3: cobalt stearate, 0.5 wt %
*4: manganese stearate, 0.5 wt % *5: zinc stearate, 0.5 wt % *6:
silver stearate, 0.5 wt % *7: silver, 0.5 wt %
It will be learned that excellent deodorizing effects against
offensive smells of amines and sulfur-containing smelling
components such as methyl mercaptane, are expressed by the
single-layer films comprising a resin composition containing a
fatty acid metal salt of any one of Ni, Cu or Co and ultrafine
metal particles having a plasmon absorption from 300 to 700 nm of
Examples 1 and 2, and by the laminated film having a layer
containing a fatty acid metal salt of any one of Ni, Cu or Co and a
layer in which are dispersed ultrafine metal particles having a
plasmon absorption over 300 to 700 nm of Example 3.
INDUSTRIAL APPLICABILITY
The adsorptive composition of the present invention is capable of
effectively absorbing amine-type smelling components due to the
fatty acid metal salt of Ni, Cu or Co and sulfur-containing
smelling components due to the ultrafine metal particles having a
plasmon absorption of from 300 to 700 nm. The adsorptive
composition can be provided in the form of various resin
compositions, such as particles, pellets, fibers, films, sheets and
containers, or in the form of coating compositions or dispersion
solutions, and can be utilized in a variety of industrial
fields.
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